Azo dyestuffs



Patented Sept. 4, 1945 UNITED STATES PATENT OFFICE 2,384,419 AZO DYESTUFFS Richard Fleischhauer and Adolf Miiller, Frankfort-onthe-Main-Fechenheim, and Carl Theo .Schultis, Bergen, near Frankfort-on the -Main, Germany, assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application July 29, 1941, Serial No. 404,508. In Germany June 24, 1940 4 Claims.

Our present invention relates to azodyestuifs, more particularly to those of the general formula:

HMIOQIMI wherein Y is as defined above, with l-a-rylamin-o- -hydroxynaphthalene-7-sulfonic acids, which are obtainable by acting with aromatic amines, advantageously in the presence of salts thereof, on 1-amino 5-hydroxy-naphthalene-'7-sulfonic acid or l-aminonaphthalene-5.7disulfonic acid, in the latter case aftertreating the primary condensation products with caustic alkalies, or by decomposing the 1-amino-5-hydroxynaphthalene-7-sulfonic acid or 1.5-dihydroxynaphthalene-7-su1fonic acid with aromatic amines in the presence of :salts of sulfurous acid.

The present azodyestufis dye the animal and cellulosic fibers, particularly cotton and viscose silk valuable shades of good fastness properties, especially bright gray shadesof a 'very good fastness to light, which are of a particular importance, or other covered shades having a grayish constituent, such as brownish, olive-greenish .or blackish shades. Since the combination with the 1 arylamino-5-hydroxynapthalene 7 sulfonic acids is advantageously carried out in a neutral or preferably alkaline medium, whereby the "azo group generally enters into the ortho-position to the hydroxy group, it is possible to convert the dyestuifs in substance or on the fiber in their metallic complex compounds, containing particularly copper or chromium, the dyeings of which are distinguished by a particular fastness to washing and mostly to light.

So far as the dyestufis contain in the nucleus signified by X in the aforesaid general formula or in an other place within the molecule the radicle of the salicylic acid group they yield very fast dyeings to washing when treated on the fiber with metal salts, particularly with chromic salts.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto, the parts being by weight and all temperatures in degrees centigrade.

Example 1 The alkaline tetrazosolution, containing sodium-carbonate, of 27.2v parts of 4.4'-diaminodiphenyl-3.3'-dicarboxylic acid is combined while cooling with a neutral solution of 31.5 parts of 1 phenylamino 5 hydroxynaphthalene-I-sulfonic acid. The formed intermediate is combined in the presence of an excess of sodium carbonate with 17.4 parts of l-phenyl-3-methyl-5-pyrazolone. The disazodyestufi thus obtained of the formula:

H000 00011 on N N=N 1i: Hols HaC-G- H 001: --N tHs is when dry a dark powder soluble in water with a dark brown and in concentrated sulfuric acid with a dark violet color and dyes cotton violet-gray shades turning to a reddish brown shade of a good fastness to light and washing when aftertreated with copper salts.

When using a second coupling component o-methoxyanilide of acetoacetic acid or other arylides thereof the formed dyestuffs dye cotton grayish brown shades turning to a brown shade when aftertreated on the fiber with copper salts.

When using as first coupling component l-(4'-methoxyphenylaminoor -methyl-phenylamino) 5 hydroXynaphthalene-7-sulfonic acid the formed dyestufis dye somewhat more covered brown shades.

One may likewise combine the tetrazocompound at first with one molecular proportion of a yellow-component such as acetoacetic acid anilide, 1-phenyl-3-methyl 5 aminopyrazole, 1-phenyl-5 pyrazolone-3-carboxylic acid, 1-(4'- sulfophenyl) -3-methyl-5pyrazo1one and combine the formed intermediate in an alkaline solution with 1 -'(4- aminodiphenylamine) 5 hydroxynaphthalene-7-sulfonic acid.

The formed dyestuffs dye when aftertreated on the fiber with copper salts yellowish to reddish brown shades of a very good fastness to light and a. particular fastness to washing.

When using as tetrazocompound 4.4'-diaminodiphenyl-3,3'-dihydroxyacetic acid dyestuffs of similar brown shades are obtained.

Example 2 with a blue and in concentrated sulfuric acid i s I with a greenish blu color and dyes cotton blue e t a pound of 33.2 parts of shades turning when aftertreated with copper diaminodiphenyl y o y ce ic ac d salts into a neutral gray of good fastness to light combined in the presence of an excess of sodium a d washing.

carbonate with 63 parts of 1-pheny1amino-5-hy- The same dyestufi may be prepared by an indroxynaphthalene-'7-sulfonic acid. The formed verse sequence of the. coupling processes.

i z y fi of the f rmula: s- When using as one coupling component other 11000151200 cornice-011 7 1 aryl'amino hydroxynaphthalene '7 10 sulfonic acids such as for instance th 4-methoxyphenylaminoor the 4-amin0diphenylamino-compound and aftertreating the dyeings obtained with the formed dyestufis on the fiber with copper salts a little more reddish neutral 5 gray shades of very good fastness particularly to washing are obtained. I

is when dry a violet-black powder soluble in wa- The particularly Valuable dyestufl of the forter with a blue and in concentrated sulfuric'acid mula:

HOOCCHaO OCHzOOOH with a. greenish blue color and dyes cotton blue is when dry a dark powder and dyes cotton blue shades turning when aftertreatedwith copper shades, turning to a gray shade of a very good salts to a neutral gray shade of a goodfastne'ss fastness to washing and light when aftertreated to water and washing and a very good fastness with copper salt. f to light. 7 s, N Y When replacing in the aforesaid combinations When using as coupling component the 1-(4- the 2'- amino-8-hydroxynaphthalene-6-sulfonic methoxyphenylaminoor -methyl-phenyl-amiacid by 1-amino-5-hydroxynaphthalene-7-su1- no) -5-hydroXynaphthalene-7-sulfonic acid the ionic acid the dyestufis obtained dye cotton when formed dyestuffs dye when aftertreated with copaftertreated with copper compounds more bluish per salts somewhat more reddish gray shades of r y had s of a similar good fastness to washgood fastness. 40 ing and a very good fastness to light, or when Example 3 replacing it by other hydroxynaphthalene comv I 1 a pounds such as 1-acetylamino-5-hydroxy-naph- When combining the tetrazo compound of 33.2 thalene or 1-(2'-carboxybenzoyl-amino) -7-hyparts of '4.4-diaminodiphenyl-3L3'-dihydroi ydroxynaphthalene the aftertreated dyeings are acetic acid with 31.5 parts of l-phenylamino-5- of a full and bluish respectively gray shade. hydroxynaphthalene-7-sulfonic acid and com bining the intermediate thus formed with 24 parts i E l 4 of 2 amino 8 hydrox'ynaphthalene-G-sulfonic acid the formed disa zodyestufi ofthe formula: The t t u d of .2 parts of Hoop c1110 v OCHzCOOH aminodiphenyl-3.3-dihydroxyacetic acid is com- OH g I g bined with 36,5 parts of 1-(4'--methoxyphenyl- In amino) -5 hydroxynaphthalene-l-su1fonic' a c i d HzN N=N N=N and the formed intermediate with 34.4 parts of SO3H V M H038 the dyestufi, obtainedby combining in an acid h q 1 medium diazobenzene withZ-amino-S-hydroxyrrrrnaphthalenefl-sulfonicacid.-

v V H Y Y Th trisazodyestufi thus obtained of the foris when dry a dark powder soluble in water mula:

' on Hoocmoo V ocrncoon scan 7 I Y H038 is when dry a dark brown powder soluble in water with a blue and in concentrated sulfuric acid with a dark green color and dyes cotton when aftertreated with copper salts fast neutral gray shades.

When combining the aforesaid intermediate with the dyestuff, obtained by combining in an acid medium 1-diazo-4-hydroxybenzene-3-carboxylic acid with 2-amino-5-hydroxynaphthalene-7-sulfonic acid the formed trisazodyestuff dyes cotton somewhat more covered gray shades.

Example The intermediate obtained according to Example 3 by combining the tetrazocompound of 33.2 parts of 4.4"-diamino-diphenyl-3.3'-dihydroxy-acetic acid with 31.5 parts of l-phenylamino-5-hydroxynaphthalene-7-sulfonic acid is further combined with a solution of 23.9 parts of 2 amino 5 hydroxynaphthalene-l-sulfonic acid in the presence of 'an excess of sodium bicarbonate. The aminodisazodyestufi thus formed is diazotized again and combined in the presence of an excess of sodium carbonat with 19.1 parts of acetoacetic acid ortho anisidide. The dyestuff thus obtained of the formula:

HOOCHICO OCHQCOOH OH OH N=N N=N N 503E HOaS NlO is when dry a dark powder soluble in water with a bluish gray, in concentrated sulfuric acid with a bluish green color and dyes cotton bluish gray shades turning when aftertreated with copper salts to a more reddish gray of a very good fastness to washing and light.

When using as final component 3-methylpyrazclone the formed dyestufi dyes cotton neutral bluish gray shades of a very good fastness to washing when aftertreated with copper salts, when using as final component a-hydroxyquinoline the aftertreated dyeing exhibits a somewhat more reddish gray shade of good fastness to washing.

When coupling the aforesaid intermediate with other diazotisable amino-hydroxy naphthalines, which may have an hydroxy group etherified by an alkyl group, such as 1-amino-5-hydroxynaphthalene-7-sulfonic acid, 2 amino 8 hydroxynaphthalene-fi-sulfonic acid, l-amino-2-ethoxy naphthalene-fi-sulfonic acid, .1 amino 7 hydroxynaphthalene-3-sulfonic acid, 1-amino-8- hydroxynaphthalene-4-sulfonic acid, 1-amino-8- hydroxynaphthalene-5-sulfonic acid, l-amino-S- hydroxynaphthalene-6-sulfonic acid, l-amino-8- hydroxynaphthalene-3.G-disulfonic acid and diazotizing the formed aminodisazodyestufis and combining with the aforesaid final components, advantageously in the presence of pyridine and sodiumbicarbonate the formed dyestufis dye, when aftertreating the dyeings with copper salts, cotton reddish to greenish to neutral gray shades of a good fastness to washing and light.

When using as middle component 23.9 parts of 2 amino-6-hydroxynaphthalene 8 sulfonic acid and as final component 19.1 parts of acetoacetic acid ortho-anisidide the formed dyestuff is soluble in water and concentrated sulfuric acid with a green color and dyes cotton, dark green shades turning to olive green shades of a very good fastness to washing and light when aftertreated with copper salts.

Example 6 The tetrazocompound of 33.2 parts of 4.4'-diaminodiphenyl-3.3 dihydroxyacetic acid is combined in the presenc of an excess of sodium carbonate with '77 parts of l-(3'-carboxyphenylamino) -5-hydroxyn aphthalene-'l-sulfonic acid. The formed dyestufi of the formula:

0 CHgC 0 OH HSO:

NIH- 3 or the corresponding l-thioglycollic acid similar dyestufis of likewise good tinctorial properties are obtained.

Example 7 The intermediate derived from 33.2 parts tetrazotized 4.4 diaminodiphenyl 3.3 dihydroxyacetic acid and 23.9 parts of 2-amino-8-hydroxynaphthalene-G-sulfonic acid is combined with 35.9 parts of 1-(3-carboxyphenyl-amino) -5-hydroxy- 'l-sulfonic acid in the presence of an excess of sodiumbicarbonate. The formed diazodyestuff of the formula:

on no'oon'gc zo oomooon" on j OOH 2. The azodyestuff of the formula:

ocnlooon Hooomoo wherein X-is a phenyl radical."

3. The azodyestufl' of the formula: 1

OGHEC O OH OH -s 01H" r Hols stuffs are obtained when using as final components which dyestufi is when dry a dark powder and the coupling components which are mentioned in the last paragraph of Example 6. r

We claim: 7 v 1. The azo.,dyestufi"s of the formula where X is a phenyl radical, Y is selected from the group consisting of COOI-I and OCH COOH brown shade of a good fastness to washing and the Ys being identical, and R represents a coupled radical selected from the group consisting of pyrazolones, amino-hydroxy naphthalenes, and aceto-acetic acidarylides, which dyestufis dye animal and cellulosic fibers shades of good fastness to light and washing.

dyes cotton blue shades turning to a gray shade of a very good fastness to washing and light when aftertreated with copper salt.

4. The azodyestufi of the formula:

Hooo COOH on -N=N N H Hols which dyestufi is when dry a dark powder and dyes cotton grayish brown shades turning to a light when aftertreated with copper salts.

RICHARD FLEISCH AUER; 1

ADOLF MULLERQ CARL 'rmt'o SCHULTISQH 

